Copolymers of a dialkyl amine oxide and a monovinylidene compound and oriented fiber thereof



COPOLYMERS OF A'DIALKYL AMINE. OXIDE AND. A MONOVINYLIDENE COMPOUNDTANDORIENTEDFIBER THEREOF, 1 t

('12 Claims. (Cl. 260-855) This: invention relates broadly to new anduseful copolymer compositions," andmore particularly to compositionscomprising'a linear copolymer produced by polymerization. of a mixtureof copolymerizable ingredients including essentially a bis ethylenicallyunsaturated compound containing two and only two unsaturated groupings.each having a terminal CH =C radical. Theinvention isiespeciallydirected to such compositions comprising'alinear copolymer obtained bypolymerization of a mixture oftopolymerizable ingredients" includ-' ing('1) a bis ethylenically unsaturated compound represented by the generalformula I v v CH CCH R \i CHz=(l1-CH3 O J R2 where. R1 and R eachrepresents a member of the class consisting ofhydrogen and the methylradical, and'R represents a radical'of the class consisting of saturatedaliphatic (including aromatic-substituted saturated aliphatic)hydrocarbon radicals and aromatic (including saturated aliphaticsubstituted aromatic) hydrocarbon radicals, and (2) a monoethylenicallyunsaturatedcompound which is copolyrnerizable-with the compound of (l)'and which contains a single CH =C grouping. The ingredients of (1) and(2) are present in the aforementioned mixture in the ratio offrom about0.1 to about 40 molarper cent of the former to. from about 99.9- toabout 60 molar percent of the latter. The scope of the invention also.includes method features, as well as products comprising an orientedfiber made from certain of the copolymers.

Illustrative examples of radicals represented by R in Formula-1' aresaturated aliphatic (including saturated cyclo-aliphatic), e. g.,methyl, ethyl, propylto octadecyl, inclusive, including the variousisomeric forms, cyclopentyl, cyclohexyl, cycloheptyl, etc.;aromatic-substituted saturated aliphatic, e. g., benzyl, phenylethyl,phenylpropyl, etc.; aromatic, e. g., phen'yl, biphenylyl or xenyl',naphthyl, etc.; and saturated aliphatic-substituted aromatic, e. g.,tolyl, xylyl,. ethylphenyl, tert.-,butylphenyl-, etc. It will be notedthat the examples of radicals represented by R given above include thosehydrocarbon radicals wherein there are from 1 to 18 carbon atoms in asaturated aliphatic hydrocarbon grouping thereof. Specific examples ofcompounds embraced by Formula I are:

Diallylmethylamine oxide Diallylethylamine oxide I'Dimethallylmethylamine oxide Dimethallylethylamine oxideDiallylphenylamine oxide Diallylbenzylamine oxide Diallyltolylamineoxide I Dimethallylphenylamine oxide- 7 United States Patent 2,871,229Patented Jan. 27, 19 59 ice 2 Dimethallylbenzylamine oxideDimethallyltolylamine oxide Diallylcyclohexylamine oxideDimethallylcyclohexylamine oxide Otherexamples will be apparent to thoseskilled in the art, from Formula land from the illustrative examples ofradicals represented by R H Any suitable method can be used in preparinghis ethylenically unsaturated compounds, more particularly amine oxides,of the kind embraced by Formula I. One general method of preparation isas follows:

A diallyl (or dimethallyl) tertiary amine, corresponding to the amineoxide to be prepared, is dissolved in a mixture of water and asufiicient amount of an organic solvent to solubilize the tertiaryamine. The chosen organic-solvent component of the mixture should be onewhich is inert to the action of hydrogen peroxide. Examples of suchsolventsare dioxane, acetone and form; amide. To the solution of thetertiary amine in the mixture of water and organic solvent is added onemolar equivalent, plus a suitable excess (e. g., about 10%), of hydrogenperoxide in the form of, for instance, a 50% aqueous solution. Thesolution is stirred at ro orn temperature .(20 30, C.) for a while, e.g.,v for from, 2 or 3 minutes to 2 hours or longer, and-then is allowedto stand undisturbedat room temperature for a prolonged period, forinstance for a period of from 4 to 7 days. Aliquots are titrated fromtime to time during this period, using 0.1 N ceric sulfate solution todetermine the conversion of amine to. amine oxide. Usually, afterstanding for about 5 days, the conversion of-the tertiary amine tothecorresponding amine oxide, is better than 99%. The solutionisclarified (assuch, or after prior dilution with water, as desired oras conditions may require), for instance by treatment with adecolorizing carbon or other suitable decolorizing or clarifying agent.The clarified solution can be used as such, if desired; or it canbeconcentrated to a desired point by distilling offall or part ofthewater and/ororganic solvent, using reduced pressure if the solvent isrelatively high boiling. The residue comprises the his, allyl (ormethallyl) amine oxide of the kind embraced by'Forrnula I. Ordinarily,the solvent-free amine oxide is a waxy solid. 1

It was, known prior to my invention that monoallyl amine could becopolymerized with particular proportions of acrylonitrile and withmixturesof comonomers including acrylonitrile to yield a fiber-forming(fiberformable) copolymer (see, for example, U. S. Patent No. 2,626,946dated January 27, 1953). It was also known prior to my invention thatvarious diallyl compounds, more particularly diallyl estersof certainpolycarboxylic acids (specifically fumaric, sebacic, succinic, adipicand phthalic), could be polymerized to a solid, insoluble and infusibleor cross-linked state (see, for example, U. S. Patent No. 2,311,327dated February 16, 1943). How.- ever, to the best of my knowledge andbelief, it was not known or suggested prior to my invention that linearcopolymers having particular and characteristic properties that makethem especially valuable for use in industry could be produced bycopolymerizing critical molar prQ- portions of diallylmethylamine oxide,dimethallylmethylamine oxide, or other compound (or mixture of.compounds) of the kind embraced by Formula I, with at least one compoundwhich is different therefrom, is copolymerizable therewith and whichcontains a single CH ,=,C grouping, e. g., styrene, nuclearlysubstituted monomethyl and ,dimethyl styrenes, methyl and other loweralkyl acrylates, acrylamide, acrylonitrile, methaerylonitrile, vinylacetate, etc.

It is preferred mine as the comonomer with the bis 3 I ethylenicallyunsaturated amine oxide a compound which is copolymerizable therewithand which is represented by the general formula and alkaryl radicals andradicals represented by the formulas where R and R each represents aradical selected from the class consisting of alkyl and alkoxyradicals,'R represents a radical selected from the class consisting ofalkyl and aryl radicals, R and R each represents a member of the classconsisting of hydrogen, and alkyl, aryl, alkaryl and aralkyl radicals,and R has the same meaning as 'R5 and R6.

' The present invention is based on my discovery that compositionscomprising new and useful linear copolymers can be produced bypolymerization of a mixture of particular molar proportions of a bisethylenically unsaturated amine oxide of the kind embraced by Formula Iand a monoethylenically unsaturated compound which is copolymerizablewith the aforementioned bis compound and which contains a single CH =Cgrouping. The comonomer which is copolymerizable with thebisethylenically unsaturated compound is preferably one which isrepresented by Formula II. The molar percentages of the aforesaid biscompound and comonomer which is copolymerized therewith may beconsiderably varied within the range of from about 0.1 to about 40 molarpercent, e. g., from 0.5-2 to -30 molar percent, of the compoundembraced by Formula I (specific examples of which have been givenhereinbefore) to from about'99.9 to about 60molar percent of thecomonomer containing a single CH =C grouping, e. g.,- from 9899.5 to7080 molar percent of the said CH =C compound. The copolymerizationreaction may be carried out in any suitable manner, but preferably iseifected while the mixture of copolymerizable ingredients is dissolvedor dispersed in an aqueous medium and with the aid of a polymerizationcatalyst, after which the linear copolymer that is formed is isolated,if desired, from the aqueous mass; or, in those cases where thecopolymer is formed in solution, the solution of the copolymer incertain cases may be used directly as such without isolation of thecopolymer from the aqueous mass.

It was quite surprising and unexpected that a bis ethylenicallyunsaturated amine oxide containing two unsaturated groups having aterminal CH =C radical, that is, a compound embraced by Formula I, couldbe copolymerized with another compound containing a single CH =Cgrouping to yield a linear copolymer, since ordinarily it would beexpected that such a his compound when copolymerized with a compoundcontaining a single CH =C groupingwould yield across-linked copolymer.The reason for this monofunctionality of a bis ethylenically unsaturatedcompound of the kind used in practicing this invention is not fullyunderstood.

Surprisingly, it was also discovered that the presence of the secondethylenically unsaturated grouping (allyl or methallyl radical) on thenitrogen atom apparently increases the susceptibility of the firstethylenically unsaturated grouping to copolymerization with a compoundcontaining a single CH =C grouping.

The properties of the copolymers obtained by practicing the presentinvention arequite unusual and in no way could have been predicted fromthe properties of the monomers employed in their preparation or fromknowledge of the properties of simple homopolymers produced from theindividual monomers. As a result, the characteristicproperties of thenew linear copolymers of the invention make them eminently suitable foruse in industry in applications where the simple homopolymers thereof,as well as other, types of copolymers, would be entirely unsuited. Forexample, the copolymers of a minor molar percentage of a bisethylenically unsaturated compound of the kind embraced by Formula I anda major molar percentage of acrylonitrile (e. g., at least mole per centof combined acrylonitrile) yield a fiber-forming linear copolymer whichis more receptive to dyes, especially acid dyes, than the homopolymer ofacrylonitrile and many of the fiber-forming copolymers of acrylonitrile.Thus, one can make products 'comprising an oriented fiber comprised ofalinear copolymer obtained by polymerization of a mixture ofcopolymerizable ,inegridents including (1) a bis ethylenicallyunsaturated compound of the kind embraced by Formula I, e. g.,diallylmethylamine oxide, diallylethylamine oxide, etc., and (2)acrylonitrile, the ingredients of (1) and (2) being present in theaforementioned mixture in the ratio of from 2 to 20 (e. g., from 5 to15) molar percent of the former to from 98 to 80 (e. g., from 95 tomolar percent of the latter.

Copolymers of acrylamide and his ethylenically unsaturated compounds ofthe kind used in practicing this invention also have very valuableproperties. For'example, such copolymers can be used as textile-treatingagents, e. g., in rendering wool-containing fabrics resistant to feltingand shrinking, as core binders, in adhesive and laminating compositions,as thickeningagents; in the photographic arts and for many otherpurposes.

The linear copolymers of this invention also maybe used asintermediatesin the preparation of other synthetic compositions. For example, theacrylamide copolymers having at least one hydrogen atom attached to theamino nitrogen atom can bereacted with an aldehyde, e. g., formaldehyde,to yield a new class ofthermosetting or potentially thermosettingresinous compositions. Or, thermosetting or potentially thermosettingcompositions also may be produced from 'any of the linear copolymers ofthe invention by cross-linking the linear copolymer through the residualallyl (or methallyl) grouping, for instance, by copolymerization with asuitable cross-linking-agent, e. g., diallyl phthalate; diallylsuccinate; any'of the known polymerizable unsaturated alkyd resinscontaining a plurality of alpha, beta-enal groups; etc. Such acopolymerization with a cross-linking agent advantageously is efiectedat an elevated temperature and with the aid of a polymerizationcatalyst.

Polymerization catalysts which are suitable for use-inpolymerizing'compounds containing an ethylenically unsaturated grouping,specifically a vinyl grouping, are usually suitable for use in producingthe new linear copolymers of the present invention. Catalysts which areespecially suitable for use in practicing this invention are thewater-soluble peroxy catalysts,-preferably a watersoluble salt ofpersulfuric .(perdisulfuric') acid, which salt is preferably used-- incombination with a sulfoxy type of reducing agent. Other examplesof'polymerization catalysts which are useful in practicing the presentinvention include the inorganic and organic peroxides, e, g., the diacylperoxides, the'primary, secondary and tertiary alkyllperoxidesandhydroperoxides and esters thereof, the various water-solubleperacetate's, -perchlo rates, percarbonates, perbo'rates, perphosphates,e. g., the

7 compounds which engender sulfurous acid, e. g., alk'ali metalsulfites,'ethyl and other alkyl .sulfites', etc.'), .various organicsulfinic acids, e. g., :p-toluene sulfinic' acid, formamidine sulfinicacid, etc. e. g., sodium sulfite, or similar compounds which engendersulfurous acid are used, the aqueous solution also' should contain astrong acid, e.i g.,sulfuric acid,-etc.', in an amount which is at leastchemically equivalent to the amount of such a compounden-genderingsulfurous acid that is employed.

If alkali-metal sulfites,

Various other free. radical;types of catalysts can be used to acceleratepolymerization, e. g., alpha, alphaazodiisobutyronitrile. Illustrativeexamples of other cat- .alysts that can be employed are given in, forinstance, U; S. Patent No. 2,656,339. I

The concentration of the catalyst is-relatively small, e g., from, byweight, about 1 part, of catalyst .per 1000 paIts'of the monomericmixture to about 4 or 5 parts of catalyst per 100 parts of the mixtureof monomers. The

amount ofapolymerization adjuvant or.-activa,t0r used likewise may bevaried considerably, but generally is within therangeof from about 0.1to1 molarproportion based. on the catalyst used or an amount which ischemically equivalent to the amount of catalyst employed; The use ofhigher ratios of activatorwith respect-to the catalyst is not precluded,e. g., 2 or 3 or more moles of activa-' tor .per mole of catalyst, orcorrespondinglylarger proportions on a chemical equivalent basis, but noparticular advantages ordinarily accrue therefrom.

The mixture of monomers can be polymerized in emulsion or solution stateto yielda linear copolymer. Good results are obtained by eifectingcopolymerization while the monomers are dissolved in a suitable-solvent,preferably water or. liquid'solvent comprising mainly water. Suitableinert organic solvents also can be used advantageously in some cases, e.g., benzene, .toluene, xylene, various ketones, etc. The polymerizationreaction ad vantageously is conducted under a blanket of 'an inert gas,e.g., nitrogen gas. a

The temperature at which the monomers are 'copolymerized can beconsiderably varied,-.but inmost cases the polymerization temperaturewill be within the range of -about '2030 6., preferably at least 35. or40 :0, up to the boiling temperature of the mixture of monomers,depending, for example, upon; the particular catalyst, if any, used, therapidity of polymerizationn ,wanted and otherinfluencing factors. i

. The polymerization can 'be carried out continuously, semi-continuouslyor by batch operations. It canbe effected under superatmosphericpressure if desired or required.

7 In order that those skillcd in the art may better understand how thepresentinvention can be carried into effect, the following examples aregiven by way of illustration and notbyway of limitation. In all-casestheparts and percentages are by-weight unless otherwise stated. ExamplesA, B, C and D, which follow, are illustrative of how specific bisethylenically unsaturated amine oxides of the kind embraced by FormulaIcan be prepared. K

EXAMPLE A Preparation of dial lylme thylamine oxide A reaction vessel ischarged with 33 g. (0.3 mole) of diallylmethylamine, 21.4 g. (0.315mole) of a 50% aqueous solution of hydrogen peroxide, 336 ml. of water,and .200 ml. of acetone. The mixture is vigorously agitated until aclear solution is obtained, and thereafter it is allowed to standundisturbed at room temperature (about 30 C.) for 5 days. It is thenconcentrated in an air stream to a'total volume of 350 ml. This solutionis clarified by treatment with a finely divided decolorizing carbon. Thecarbon is filtered OE, and to the filtrate is added 31.2 ml. of aaqueous solution of hydrogen peroxide, This mixture is then diluted toa. total volume of 362 ml. (10% solids). Titrations of aliquots ofthismixture that are made during the next four days, using 0.1 N cericsulfate solution, indicate the conversion to be constant at about 99.7%of the theoretical. This 10% aqueous solution of the linear copolymercan be used in this form in aqueous copoly merizations withrnonoethylenically unsaturated monomers of: the kind and in the amountused in practicing this invention; or it can be concentrated to anydesired extent as'has been described hereinbefore.

EXAMPLE B Preparation of diallylethylamine oxide The same generalprocedure is followed as described under Example A withthe exceptionthat 0.3 mole of diallylethylamine is used instead of 0.3 moleofdiallylmethylamine.

EQAMPLE C e Preparation of dimethallylmethylamine oxide The same generalprocedure is followed as described under Example A with the exceptionthat 0.3 mole of dimethylallylmethylamine is employed in-place of 0.3mole of diallylmethylamine. v

EXAMPLE D Preparation of dia'llylbenzylamine oxide The same generalprocedure is followed as described under Example A with the exceptionthat 0.3 mole 'of diallylbenzylamine is used instead.of 0.3 mole ofdiallylmethylamine. a

EXAMPLE 1 e "Copolymer of acrylamide and diallylmethylamint oxide A3-necked reaction vessel is equipped with a ther- 'rnorneter, mechanicalstirrer, gas-inlet tube, reflux condenser, and three dropping funnels,which are hereinafter designated for convenience as A, B and C. Thevessel is charged with a solution of 50 g. (about 2.9 mole percent) ofdiallylmethylamine oxide in 500 ml. of water, the solution is adjustedto pH 2 with 6 N sulfuric acid, and the mixture is swept With nitrogenfor 20 minutes. Funnel A is charged with a' solution containing 900 g.(about 94.2 mole percent) of acrylamide and 50 g." (about 2.9 molepercent) of diallylmethylamine oxide dissolved in 2500 ml; of Water.This solution is adjusted to pH 2 with 6 N sulfuric acid. Funnel Bischarged with a solution containing 2 g. of ammonium persulfate dissolvedin 500 ml. of water. Funnel C is charged with a solution containing 1 g.of potassium meta-bisulfite dissolved in 500 ml. of Water. The contentsof the dropping funnels are added portionwise, in constant proportion toone another, over a 30-minute period at 40 C. while stirring. Thereaction mass is heated for 3 hours at the same temperature (40 C.).' Asteady flow of nitrogen gas is kept running through the reaction set-upduring the polymerization. The resulting viscous solution )Of linear.copolymer of acrylamide and diallylmethylamine oxide is diluted byadding 10,000 ml. of

water, accompanied by vigorous stirring, to yield a solution containing10% copolymer solids. I

As the product is a free-flowing solution and contains no'cross-linkedmaterial visible to the naked eye, the composition of the copolymerproperly may be considered to be essentially the same as the chargecomposition.

To 80 g. of the above 10% solids solution of theacrylamide-diallylrnethylamine oxide linear copolymer is added 80 g. ofwater, and the resulting solution is adjusted to pH 10 by the additionof a few drops of 2.3 N sodium hydroxide. To this solution is added 10.5g. of formalin (approximately 37% aqueous formaldehyde solution),previously adjusted to pH 10, and 1 the resulting mixture is heated for1 /2 hours at 50 C., after whichhydrochloricacid is added in an amountsulficient to lower the pH to 7.

A piece of woolen goods is immersed in the above solution. The treatedwool is passed through squeeze rolls, after which it is framed,air-dried for a short period, and then heated for 9 minutes at 290 F.After cooling to room temperature, the sample is removed from the frame,allowed to remain undisturbed for about 16 hours, and is then measuredprior to laundering. The method of laundering is a modification of thestandard method of the A. A. T. T. C., and involves heating for 2030minutes at 240 F. while drying after each washing. After a cycle of .5washing (10 minutes in soap solution) and drying operations, the dried,treated cloth shows a shrinkage of only 5.1%.' After cycles of washingand drying operations and a washing of 1 hour insoap solution after eachcycle, the dried, treated cloth shows a shrinkage of only 8.2%. Inmarked contrast, untreated woolen cloth after 5 washing cycles ofminutes each followed by 60 minutes washing shows a shrinkage of 45%.

EXAMPLE 2 Copolymer of acrylamide and diallylethylamine oxide Theapparatus used and procedure followed are, in general, the same as thatdescribed in Example 1 with the exception that the reaction vessel. isprovided with a fourth dropping funnel, D. The polymerization vessel ischarged with 30 g. (about 8.2 mole percent) of diallylethylamine oxideand 720 g. of water, and the solution is adjusted to pH 2.5 by theaddition of 5 N sulfuric acid. Funnel A is charged with 170 g. ofacrylamide (about 91.8 mole percent) dissolved in 580 g. of water.Funnel B is charged with 2 g. of ammonium persulfate dissolved in 250 g.of water. Funnel C is charged with 1 g. of potassium meta-bisulfite in250 g.

of water. 1 Funnel D is charged with 50 ml. of isopropanoL- The reactionvessel is purged with nitrogen for one hour, with stirring. The contentsof the four funnels are added in five equal portions with a minuteinterval between each addition. Stirring is maintained continuously asis a continual, slow flow of nitrogen into the vessel. The temperatureis held at 40 C. throughout the 80-minute addition period, and thesubsequent heating period of 3 hours.

Aqueous solutions of the linear copolymer of acrylamide anddiallylethylamine oxide of this example, or aqueous solutions of theirformaldehyde-reaction products, are useful as, for instance, corebinders, components of adhesive and laminating compositions, sealingagents, thickeners, etc. They are also useful as textiletreatingcompositions or as components of such compositions. For instance, theycan be employed in treat ing wool-containing fabrics and other textilesto impart shrinkage resistance thereto as described under Example 1 withreference to the formaldehyde-reaction product of that example; or,solutions of formaldehyde-reaction products of the coplymer can be usedin this same manner. r i

For the acrylamide used in Examples l and2, one can substitute anequivalent amount of another monomer (or mixture of monomers in anyproportions) which is different from diallylrnethylamine oxide (ordiallyl-- ethylamine oxide), is copolymerizable therewith and whichcontains a CH ==C grouping, more particu-- larly a compound (or mixtureof compoundsfof the: kind embracedby Formula II, e. g., methacrylamide,.

' .a copolymer of, for instance, diallylrnethylamine oxide (ordimethallylmethylamine oxide) and, for example,N-tertiary-butylacrylamide.

For thediallylmethylamine oxide ofv Example 1 or the diallylethylamineoxide of Example-2, oneucanz'substitute an equivalent amount of thecorresponding dimethallylmethylamine oxide, dimethallylethylamine oxideor any other compound of the kind embraced by Formula I, numerousexamples of which have been given hereinbefore.. i i i EXAMPLE 3copolymer of acrylonitrile and dially lmethylamine Oxide Y Theapp'aratusused is essentially the same as that described in Example 1 with theexception that only two dropping funnels are employed. To the vessel isadded 98.5 g. of 96.9% acrylonitrile (about 97.4 mole percent), 6.1 g.-of diallylrnethylamine oxide (about 2.6 mole percent), and 800- g. ofwater. The solution is adjusted to pH 2 by the addition of 5.0 ml. of 3N HNO and then 140 g. of water is added. To the first funnel is added asolution of 0.44 g. of sodium chlorate and 3.15 g. of disodium sulfiteheptahydrate dissolved in 100 g. of water. To the second funnel is added6.2 ml. of 3 N HNOg and 94 ml. of water. As usual, the reaction set-upis swept with a stream of nitrogen for 30 minutes-prior to the start ofthe copolymerization, and the reaction is carried out under a nitrogenstream. The constant-temperature bath is set at 40 C. A 40-ml. additionis made from each funnel during vigorous stirring. After a few minutes,a white solid is observed precipitating from solution. The remainder ofeach of the solutions in the dropping funnels is added in six portionsover a 2 /2-hour period, followed by a 2-hour heating period at 40 C.The linear copolymer of acrylonitrile and diallylrnethylamine oxide thatforms is filtered from the reaction mass, washed with 2 liters of Water,and driedat 70 C. A fairly good yield (about 70% of the theoretical) ofthe dried copolymer is obtained. It is soluble in dimethylformamide andother organic .solvents, as well as in a concentrated aqueous solutionof a water-soluble salt which yields highly hydrated ions in an aqueoussolution, e. g., sodium, potassium and calcium thiocyanates, guanidinethiocyanate, zinc chloride, etc.

One-half gram of dried copolymer is dissolved in 50 ml. ofdimethylformamide to yield a perfectly clear solution without anyindication of insoluble gel being present. This would indicate a lackofcross-linked material in the copolymer. A sample of the dried copolymerweighing approximately -1- g. is dispersed in a mixture containing 10ml. of a 10% solution of sodium sulfate, 10 ml. of a 2% aqueous solutionof sulfuric acid, 10 ml. of a 2% aqueous solution of Calcocid AlizarineBlue SAPG (Color Index No. 1054), and ml. of water. The dispersion isboiled for 40 minutes, then filtered by suction, and the solid is washedwith hot water until the filtrate is colorless. The copolymer is foundto be dyed a deep blue, indicating that a substantial quantity ofdiallylmethylamine oxide has been incorporated in the copolysolution isrefluxed-on asteambathfgfZ-fhoUl's.

men Homopolymericacrylonitrile, when similarly treat- 'ed,,;is-colorl ess or nearly so. v

EXAMPLE 4 Copolymer of herylonitrfle and "dially letiz ylamine oxide Areaction vessel provided with a reflux condenser is charged with 1 80 g.(about-95.8 mole percent) of a'crylonitrile, 20 g. (about 4.2 molepercent) of diallylethylamine oxide, 750 ml. of benzene, and 2 g. ofalpha, alphaazodiisobutyronitrile (polymerization catalyst). This Theresulting linear copolymerof acrylonitrile and diallyl ethylamine oxideisfiltered off, washed with acetone and air-dried. The d'ried,amorph0,us copolymer is cream- -colored andis completely soluble indimethylformamide;

A portion of the copolymer is .made intoafiber as described in Example5.

, EXAMPLE 5 I Forty (40) parts ofthe binary polymer of Example '4 "isslurried-by rapid stirring at room temperature in 160 parts ofdimethylformamide. While protected. by a blanket of carbon dioxide thetemperature of the mixture is raised to 80 C. with slow' stirringuntilall of the copolymer has dissolved to formia clear, viscoussolution. v

After ffiltration and deaerationthe .Warm solution is extrudeddownwardly through a spinnerette having 40 holes, each 70 microns indiameter, into a spinning cell, the inner wall of whichismaintained rata temperature of approximately 425 C. by means of a fluid heating mediumwhich .circulates around the outer wall of the cell. A .current ofpreheated gas at 125 C. is introduced at the bottom of the cell and,passes upwardly counter-current to the filar'nents which passdownwardly from the spinnerette. By this means the major proportion ofthe dimethylformamide isevaporated from the filaments ;by the time thefilaments have reached the bottom of the cell.

From the bottom of the cell the group of filaments or thread is ledthrough Water to remove the .lastof the dimethylformamide solvent, afterwhich it is continuously dried by passing it over a pair of heateddrying rolls. The dry multifilament thread is thentherm'ophasticallystretched by conducting it through a slotwhich is mainthan that of theunstretched thread. To remove residual strains or shrinkage, the threadis conducted through a second, heated slot at 400 C. and thence to apairof rolls, the surface speed of which is adjusted to;permit aboutshrinkage of the thread in the slot. After this thermoplastictreatment'the thread is collected on a ring-twister bobbin. I

A skein of the finished thread is tested for its dyeability, incomparison with a skein of thread similarly prepared from homopolymericacrylonitrile, as follows:

Each skein 10 parts) is placed inadye bath consisting of 500 parts of anaqueous solution containing 0.2 part of concentrated sulfuric acid, 1part of sodium sulfate and 0.2 part of Calcocid Alizarine Blue SAPG(Color Index No. 1054). The dye bath is boiled for 30 minutes, afterwhich the skeins are removed from the bath and washed with hot wateruntil .the water is free of dye. The skein of thread of homopolymericacrylonitrile is substantially undyed while the skein of thread ofthe,copolyrnerfloflExample dyed blue.

10 Other -;p roperties of. .the thread of i copolyme'r,: .suchx-aswet-and dry tenacities',?elongation,;abrasion resistance,

'etc., .are substantially the-same as those which characmole-percent ofacrylamide and 2 mole percent of diallylbenzylamine oxide in essentiallythe samer'n'an'ner as described under Example 2. The resulting'copolymer solution is diluted to 11.3% solids.'fA-visco'sity'm'easurementlot the diluted solution is ofi the 'scale'ofthe Brookfield viscosimeter on the high sidefanjcl thus is over 100,000cps. The '1l.3%'solution almost gelatinous while cold but fluid whenheated. .It is usefuhtor instance, in preventing sedimentation of finelyfdivided materials, e. g., silver halides; in preparing compositionsthat can be employed as vehicles for the preparation of light-sensitiveemulsions; or in applications where other soluble .polyelectrolytes arecommonly employed{' v EXAMPLE 7 Cojpolymer of-styrene anddiallymethyldntirteoxide To 30,parts of diallylmethylamine oxide (about33.0

-mole percent) dissolved in 1 10- vparts of water is added (about 67.0mole percent). Thecontents of the three dropping funnels are addedsimultaneously and at equal rates over a 1-hour period with vigorousstirring. The

pot temperature is maintained at 42 C. Stirring is'con- 'tinued for 2additional hours at a temperature of 4 2 C.,

after which any unpolymerized styrene is removed by steam distillation.A free-flowing copolymer emulsion is obtained which exhibits exceptionalstability. "The emulsion of the linear ,copolymer of styrene anddiallyl- 'rnethylamine oxide is not broken by the addition of alum orsodium sulfate, by boiling, heating. for 1 hour,

orfreezing in a Dry-Ice bath for 2 hours. Upon evaporation to drynessand'redissolution of the residue in water, the copolymer emul'sion'isagain obtained.

The remarkable and unexpectedstability of this emulsion makes iteminently suitable for use as'ia component of wall paints, adhesives,and coating and/or impregnating compositions. This copolymeric emulsionor'latex also can be employeddirectlytor the preparation of varioussheets, coatings and elastomeric articles.

Instead of styrene employed inthis example, one can use an equivalentamount of, for example, para-methyl styrene, alpha, par'a-dimethylstyrene, any of the nuclearly substituted dialkyl styrenes, the variouschloroandcyano substituted styrenes and other compounds which aredifferent from diallymethylamine. oxide-tare copolymerizable therewithand containa single CH :C

grouping.

EXAMPLE 8 v Copolymer of melhyZ-acrylate and diallylmethylamine I oxideTo 6.5 g. of diallymethylamine oxide (about 31.2 mole percent) dissolvedin 21 g. of water is added 9.7 g'. of methylacr'ylate (about 68.8 molepercent), 300 g. of

water,' 0.2 g. of sodium chlorate, 1.4 g. of sodium sulfit'eheptahydrate, and the homogeneous solution is adjusted 'to pH 2 by theadditionof a few ml. of 3 N nitric acid. -The-s olution is heated at. 65C. for 3 hours. -tity of: rubbery,water-insoluble linear copolymer of Aquan- ;and sizes (e. g., textile sizes, leather-finishingcompositiQnsQetcJ), as a modifier of other synthetic resins, as acomponent of printing pastes, as an intermediate in producing othersynthetic materials, and for other purposes.

'Instead of methyl acrylate employed in this example, one can use anequivalent amount of any of the other alkyl'acr'ylates andmethacrylates, especially the lower alkyl'ac'rylates and methacrylates,e. g., ethyl, propyl, butyl and amyl acrylates, and the methyl to amyl,inclusive,- methacrylates; also, the correspondingalpha-chloroacrylates.

In amanner similar to that described above with reference to the'preparation of a copolymer of methyl acryla'te and'diallylmethylamine.oxide, one can prepare a copolymer of methyl isopropenyl ketone anddiallylmethylamine oxide, using a chemically equivalent amount of methylisopropenyl ketone for the amount of methyl acrylate used in Example 8.Instead of methyl isopropenyl ketone one can use an equivalent of, forexample, methyl, ethyl, propyl or isobutyl vinyl ketone, phenyl vinylketone or ethyl isopropenyl ketone; or any of the vinyl alkyl ethers, e.g., methyl, ethyl, isopropyl, n-butyl, isobutyl or 2-ethylhexyl vinylether;

EXAMPLE 9 Copolymer of vinyl acetate and diallylethylamine oxide To 7.5g. of diallylethylamine oxide (about 32.1 mole percent) dissolved in 22g. of water is added 9.7 g. of

'vinyl acetate (about 67.9 mole percent), 200 g. of water,

3.0g. of a 35% solution of stear-amidopropyl-beta-hydroxyethylammoniumchloride (wetting agent), 0.5 g. of sodium lauryl sulfate, 0.2 g. ofammonium persulfate, 0.1 g. of potassium meta-bisulfite, and themixture, after vigorous shaking, is adjusted to pH 2 with 3 N nitricacid. The cloudy emulsion is heatedwith occasional shaking for .3 hoursat 65 C. On the following day it is noted that addition of the reactionmixture to water yields a quantity of a white, rubbery, water-insoluble,linear'copolymer of vinyl acetate and diallylethylamine oxide. Thecopolymer is filtered ofi, Washed with water and dried at roomtemperature to a constant Weight. It can be used, for example, as anadhesive composition or as a component of such compositions.

Instead of vinyl acetate employed in this example, one can use anequivalent amount of, for example, vinyl propionate, butyrate,isobutyrate, or laurate. Instead of diallylethylamine oxide one can usean equivalent amount of other amine oxides of the kind embraced byFormula I, for instance ,diallylmethylamine oxide,dimethallylmethylamine oxide or dimethallylethylamine oxide.

EXAMPLE 10 Preparation of ternary polymer of acrylamfde, acrylic acidand dimethallylmethylamine oxide Into a 3-necked reaction vesselequipped with two dropping funnels, thermometer, stirrer and an inletfor the introduction of'nitrogen gas is charged a mixture of 1 part ofdimethallylmethylamine oxide (about 3.34 mole percent) in 57 partsofwater. The system is purged for 1 hour with prepurified nitrogen gas.One dropping funnel is charged with a mixture of 3 parts of acrylic acid(about 19.64 mole percent) and 11.6 parts of acrylamide (about 77.02mole percent) which has been neutralized to a pH of 7 with a base, and34 parts of water. Equal portions of the contents of each of thedropping funnels are added to the reaction vessel every minutes overaperiOd f V2 hour, at the end of which time the .weight (Staudingermethod) is about 79,500.

12 last addition'has been made. The temperature of the reaction mass ismaintained at",70"---C.throughout the reaction period. 1 The flow ofnitrogen gas through the system is'continued during'the entire reactionperiod. After thecontentsof the two dropping'funnels has all been addedto the reaction vessel, the reaction is permitted to continue for anadditional 3% hours. The resulting: aque'ous solution of alinear ternarypolymer of acrylamide, acrylic acid and dimethallylmethylamine oxide issuitable for such uses as described under Exampics 1, 2 and 6 withreference to the copolymers of those EXAMPLE 11 Ternary polymer ofacrylonitrile,.vinyl acetate and diallylmethylamine oxide A reactionvessel, provided with two dropping funnels, is charged with 93.0 g.. of96.9% acrylonitrile (about 92.2 mole percent), 5.3 g. of vinyl acetate(about 3.3 mole percent), 106 ml. of a 10% aqueous solution ofdiallylmethylamine oxide (about'4.5 mole percent), 10.6 g. ofsodiumvnitrate, 850 ml. ofdeionized water, and 22 ml. of 3N nitric acid.The pH of the resulting solution is 3.2; Funnel A is charged with 0.880g. of sodium chlorate and 3.15 g. of sodium sulfite dissolved in ml. ofWater. Funnel B is charged with 12 ml. of 3 N nitric acid in 88 ml. of.water. The reaction vessel and its contents are purged with nitrogengas for /2 hour beforeadditions of catalysts are begun. The pottemperature is raised't'o 40 'C. and held at that temperature throughoutthe polymerization. The contents of the funnels are added portionwiseover a 2 /2-hour period followed by a l /z-hour heating period to insurecompletenessof reaction. The white, amorphous, linear, ternary polymerof acrylonitrile, vinyl acetate and diallylmethy lamine oxide isfiltered otf, washed and oven-dried at 70 C. It weighs 68 g. (64%conversion). The molecular This ternary polymer shows good receptivitytoward and acid dye, specifically Calcocid Alizarine Blue SAPG', whentested as described-under Example 3. It is dyed a deep blue.

EXAMPLE 12 Forty-nine (49) g. of the linear ternary polymer ofacrylonitrile, vinyl acetate and diallylmethylamine oxide of Example 11,59 ml. of water and 382 g. of a 57.5% aqueous solution of sodiumthiocyanate are mixed to dissolve the polymer and to form a spinningsolution. This ,vancing in a helical path. The fiber is rinsed withwater on the rolls to remove excess thiocyanate. The washed fiber isstretchedLabout 550% While passing through a bath of hot watermaintained at a temperature of about 995 C., and then is taken up on abobbin where it is kept in a gelled state by applying a fine spray ofwater While the'fiber is being collected on the bobbin. It can beair-dried, oven-dried (for instance, under controlled conditions oftemperature and humidity), or dried by passing it in a helical 'pathovera pair of heated, converging drying rolls. The sticking temperature ofthe dried, oriented fiber is 287 C.

A S-gram swatch of the above-described, dried fiber (Sample A) and aS-gram swatch of a dried fiber similarly made from homopolymericacrylonitrile (Sample B) are immersed in a dye bath consisting of 500parts of an aqueous solution co-ntaining'0.2 part of concentratedsulfurie acid, 1 part of sodium sulfate and 0.2 part of CalcocidAliza'rine' Blue'SAPG (Color Index No. 1054).

a deep blue color while the Sample B swatch is undyed.

EXAMPLE 13 The linear, ternary polymer of acrylonitrile, vinyl acetateand diallylmethylamine oxide of Example 11 is made into a spinningsolution and thence into a fiber in essentially the same mannerdescribed under Example 12 with the following exceptions: The washedthread is stretched about 650% (instead of about 550% as in Example 12)while passing through the 99.5 C. stretch bath, andthe thread is driedby passing it continuously in a helical path over a pair of electricallyheated, converging drying rolls. Finally, it is thermally relaxed 15%.The filamentary material shows only slight shrinkage (about 0.7%) inboiling water, and the dyeing characteristics are essentially the sameas those of the product of Example 12. Other properties are generallythe same as those obtained by similarly spinning homopolymericacrylonitrile.

In a manner similar to that described above with reference to theproduction of the copolymers of the individual examples, one can preparelinear copolymers of other compounds embraced by Formula I and amonoethylenically unsaturated compound which is copolymerizabletherewith and which contains a single CH =C grouping, using theingredients in the molar percentage proportions hereinbefore described.

I claim:

1. A composition comprising a linear copolymeric reaction product of amixture of copolymerizable ingredients including (1) a bis ethylenicallyunsaturated compound represented by the general formula where R; and Reach represents a member of the class consisting of hydrogen and themethyl radical, and R represents a radical of the class consisting ofsaturated aliphatic hydrocarbon radicals, said radicals having from 1 to18 carbon atoms in the saturated aliphatic hydrocarbon grouping thereof,and aromatic hydrocarbon radicals, and (2) a monoethylenicallyunsaturated com- 2. A composition as in claim 1 wherein the bisethylenically unsaturated compound of (1) is diallyhnethylamine oxide.

3. A compostion as in claim 1 wherein the his ethylenically unsaturatedcompound of (1) is diallylethylamine oxide.

4. A composition as in claim 1 wherein the compound of (2) is amonovinyl compound.

'5. A composition as in claim 4 wherein the monovinyl compound of (2) isa monovinyl aromatic compound.

6. A composition as in claim 5 wherein the monovinyl aromatic compoundis styrene.

7. A composition as in claim 4 wherein the monovinyl compound of (2) isa monovinyl aliphatic compound.

8. A composition as in claim 7 wherein the monovinyl aliphatic compoundis acrylonitrile.

9. A composition as in claim 7 wherein the monovinyl aliphatic compoundis acrylamide.

10. A composition as in claim 7 wherein the monovinyl aliphatic compoundis a monovinyl ester.

11. A composition as in claim 10 wherein the monovinyl ester is vinylacetate.

12. A product comprising an oriented fiber comprised of a linearcopolymeric reaction product of a mixture of copolymerizable ingredientsincluding (1) a bis ethylenically unsaturated compound represented bythe general formula R1 CHF-CHI Ra where R, and R each represents amember of the class consisting of hydrogen and the methyl radical, and Rrepresents a radical of the class consisting of saturated aliphatichydrocarbon radicals, said radicals having from 1 to 18 carbon atoms inthe saturated aliphatic hydrocarbon grouping thereof, and aromatichydrocarbon radicals, and (2) acrylonitrile, the ingredients of (1) and(2) being present in the aforementioned mixture in the ratio of from 2to 20 molar percent of the former to from 98 to molar percent of thelatter;

References Cited in the file of this patent UNITED STATES PATENTS2,456,428 Parker Dec. 14, 1948 2,586,238 Lytton Feb. 19, 1952 2,700,027Bruson Jan. 18,, 1955

1. A COMPOSITION COMPRISING A LINEAR COPOLYMERIC REACTION PRODUCT OF AMIXTURE OF COPOLYMERIZABLE INGREDIENTS INCLUDING (1) A IS ETHYLENICALLYUNSATURATED COMPOUND REPRESENTED BY THE GENERAL FORMUAL